Startseite Effects of CaO addition on the CuW composite containing micro- and nano-sized tungsten particles synthesized via aluminothermic coupling with silicothermic reduction
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Effects of CaO addition on the CuW composite containing micro- and nano-sized tungsten particles synthesized via aluminothermic coupling with silicothermic reduction

  • Chu Cheng EMAIL logo , Xinyu Wang , Kexing Song , Ziwei Song , Zhihe Dou , Mengen Zhang , Haitao Liu , Xiaoheng Li und Liye Niu
Veröffentlicht/Copyright: 16. März 2023
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Nanotechnology Reviews
Aus der Zeitschrift Nanotechnology Reviews Band 12 Heft 1

Abstract

CuW composite fabricated by powder metallurgy using ultrafine metal powders as raw materials has the disadvantages such as uneven microstructure and low compactness. A novel method of synthesizing an as-cast CuW composite ingot via an aluminothermic coupling with silicothermic reduction is presented; a low-melting-point CaO–Al2O3–SiO2 slag is formed by adding CaO as a slag former, effectively reducing Al2O3 inclusion in the CuW composite. In this study, the effects of CaO addition on the novel synthesis of the CuW composite via the aluminothermic coupling with silicothermic reduction are investigated. The result shows that CaO affects the removal of large particles (≥6 µm) but not the removal of small particles (≤4 µm). With the increase in the ratio of CaO ranging from 0 to 1.0, the inclusions in the CuW composites gradually transform from Al2O3 to calcium aluminates, which are conducive to the separation of the metal and slag. The contents of Si and O in the CuW composites gradually decrease from 9.40 and 14.00% to 6.10 and 3.50%, respectively, while those of Al and Ca gradually increase from 2.54 and 0.02% to 3.83 and 0.26%, respectively.

Abbreviations

EDS

energy-dispersive X-ray spectroscopy

ICP

inductively coupled plasma emission spectrometry

R C/A

the molar ratio of CaO to Al2O3

SEM

scanning electron microscopy

SHS

self-propagating high-temperature synthesis

T ad

adiabatic temperature

XRD

X-ray diffractometry

1 Introduction

CuW is widely used in applications such as electrical contacts for high-voltage switches, electromagnetic railgun rails, and electronic packaging materials [1,2,3]. It is typically fabricated by powder metallurgy comprising an infiltration technique and a high-temperature sintering method, using ultrafine metal powders as raw material [4,5,6]. However, it is difficult to mix evenly in the mixing process of powder metallurgy for large density difference between W (19.35 g/cm3) and Cu (8.92  g/cm3), and aggregation of superfine powders, resulting in uneven microstructure [7].

At present, most scholars at home and abroad focus on improving the microstructure and properties of CuW by preparing micro- or nano-sized CuW composite particles or adding microalloying elements, which is based on powder metallurgy [8,9]. Li et al. [10], Lee et al. [11], Wang et al. [12], and Liang et al. [13] have devoted themselves to preparing micro- or nano-sized CuW composite particles using mechanical alloying and chemical processes, such as high-performance ball milling, mechanical–thermochemical, chemical coprecipitation, and sol–gel methods. Then, the CuW composite particles are sintered to prepare a composite with a tungsten grain size of approximately 2 µm and a relative density of >99.0%. The studies conducted by Johnson and German [14], Cao et al. [15], Yang et al. [16], Wang et al. [17], and Bai et al. [18] have demonstrated that a finite solid solution with Cu can be produced by adding small amounts of Fe, Co, Ni, and Cr as activated elements during sintering, and the products can be precipitated, producing intermetallic compounds at grain boundaries, which can promote the densification of W and improve the compactness of the CuW composites. In conclusion, the aforementioned methods can effectively improve the compactness and homogenize the microstructure of CuW. However, some of them increase the complexity of the preparation process of micro–nano-CuW composite powder [19]. In conclusion, the preparation of ultrafine tungsten particles uniformly dispersed in copper is the key to overcoming the nonuniform microstructure and low compactness of CuW prepared by powder metallurgy.

Aiming at improving the microstructure uniformity of the CuW composite, a novel method of synthesizing the as-cast CuW composite ingot, containing micro- and nano-sized W particles, via an aluminothermic reduction, is presented [20,21,22]. In this method, CuO and WO3 as raw materials are reduced using Al powder to obtain high-temperature CuW composite melt and Al2O3. Micro- and nano-sized tungsten particles are produced during the aluminothermic reduction; however, Al2O3 reacts with CaO added into the mixed raw materials, producing low-melting-point CaO–Al2O3 slag. After the self-propagating high-temperature synthesis (SHS) reaction, the metal and slag are separated owing to the differences in density; finally, a CuW ingot is obtained. However, our previous studies have shown that the CuW composite containing micro- and nano-sized W particles can be synthesized via the aluminothermic reduction; however, it contains a specific amount of high-melting-point alumina inclusion, which reduces the compactness and performance of the CuW composite [23]. This is because the thermite reduction reaction is a rapid heating and cooling process, during which part of solid alumina fails to effectively combine with CaO into a liquid slag phase and remains in the CuW composite melt; thus, it remains in the CuW composite [24,25,26]. Therefore, during the process of synthesizing CuW composite via the aluminothermic coupling with silicothermic reduction in this study, Al2O3 is first combined with SiO2 produced from aluminothermic coupling with silicothermic reduction, and thereafter, it is combined with an additive slag-forming agent, CaO, yielding a lower-melting-point CaO–Al2O3–SiO2 slag. Thus, the Al2O3 inclusion in the CuW composite is effectively reduced. The flowchart for this process is shown in Figure 1.

Figure 1 The flowchart of synthesizing the CuW composite via the aluminothermic coupling with silicothermic reduction.
Figure 1

The flowchart of synthesizing the CuW composite via the aluminothermic coupling with silicothermic reduction.

In this study, the thermodynamic equilibrium of the Al–Si–CuO–WO3–CaO system was calculated, and the effects of CaO addition on the novel synthesis of the CuW composite via the aluminothermic coupling with silicothermic reduction are investigated.

2 Experiment

2.1 Materials

WO3 (99.90 wt%, particle size: 32–38 µm) and CuO (99.50 wt%, particle size: ≤0.20 mm) were used as the raw materials. CuO was obtained from Zhengzhou Baixiang Chemical Reagent Co., Ltd., China, and WO3 was obtained from Sinopharm Chemical Reagent Co., Ltd., China. Al powder (99.5% pure, particle diameter: 0.5–3.0 mm) and Si powder (99.8% pure, particle diameter: 1.0–3.0 mm) were used as reductants. CaO (99.50% pure, particle diameter: ≤0.25 mm) was used as a slag former, which was supplied by Sinopharm Chemical Reagent Co., Ltd., China.

2.2 Experimental methods and analysis

The experiment was conducted under atmospheric pressure to synthesize a CuW50 composite. To prepare the raw materials before the synthesis, WO3, CuO, and CaO were heated in a drying oven at a temperature of 573 K for 24 h to remove water. The raw materials, including Al and Si powders, were weighed in proportion and placed in a ball mill. The tank was covered with a lid, and the reagents were mixed using a can mixer for 60 min. Thereafter, they were placed into a conical graphite reactor enclosed with magnesia lining with a volume of 10 L. Approximately 2–3 g of Mg powder was used as an easy ignition agent and placed on top of the other reagents. The Mg powder was ignited to induce SHS, and a high-temperature melt was obtained. Then, the melt was cast into a graphite crucible with a diameter of 40 mm and cooled to approximately 298 K. Finally, a CuW composite ingot with a size of Ф 32 mm × 12 mm was obtained after removing the slag on the surface. The mass ratio of CuO, WO3, Si powder, and Al powder is 1:1.008:0.143:0.277. The ratios of CaO in the ingredients can be expressed as R (C/A) (the molar ratio of CaO to Al2O3, and Al2O3 is a combustion product of the SHS reaction in theoretical stoichiometry). The R (C/A) in the experiments were 0.2, 0.6, and 1.0. Stainless steel balls with a diameter of 8 mm are used as milling balls, the ball-to-powder ratio is 1:5, and the milling speed is 250 rpm.

2.3 Calculation and analysis methods

The adiabatic temperature (T ad) and thermodynamic equilibrium of the Al–Si–CuO–WO3 and Al–Si–CuO–WO3–CaO systems with different R (C/A) were calculated using HSC 6.0. The chemical composition of the microalloying CuW composites was analyzed by inductively coupled plasma emission spectrometry (ICP, Optima 4300DV, Lehman USA), and its oxygen content was measured using an oxygen/nitrogen/hydrogen analyzer (Type G8, Bruker, Germany). The microstructure of the composite ingots and slags was characterized using optical metallographic microscopy (OLYMPUSPMG3) and scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS; SU-8010, Hitachi, Japan). The phase of the slags was analyzed by X-ray diffractometry (XRD; Model D8 Bruker Germany; working conditions: Cu Kα1, 40 kV, 40 mA, 2θ angular range of 10–90°, a scanning rate of 5°/min, and a step size of 0.2°).

3 Results and discussion

3.1 Thermodynamics

The T ad and thermodynamic equilibrium of the Al–Si–CuO–WO3 and Al–Si–CuO–WO3–CaO systems with an R (C/A) of 0.2, 0.6, and 1.0 were calculated as 2,423, 2,373, 2,301, and 2,231 K, respectively. Merzhanov [27] suggested that the system would not become self-sustaining unless T ad > 1,800 K. Therefore, it was deduced that the aforementioned systems could be produced.

According to the principle of minimum Gibbs free energy change, the thermodynamic equilibriums of the Al–Si–CuO–WO3–CaO systems with different R (C/A) were calculated, and the results are shown in Figure 2.

Figure 2 Thermodynamic equilibrium of the Al–Si–CuO–WO3–CaO system with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).
Figure 2

Thermodynamic equilibrium of the Al–Si–CuO–WO3–CaO system with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).

Figure 2(a) shows that in the Al–Si–CuO–WO3 equilibrium system, with increasing temperature, the molar percentages of Cu and W in the metallic phase decrease, while that of Si gradually increases, and this was particularly observed when the temperature exceeded 1,500 K. It indicates that high temperature was not conducive to silicothermic reduction, resulting in the increasing amount of Si residue in the CuW composite. With increasing temperature, the molar percentages of SiO2 and Al2O3 in the slag phase gradually decreased, while the molar percentages of mullite (3Al2O3·2SiO2) with a melting point of 2,083 K gradually increased. It was mainly due to the favorable combination of SiO2 and Al2O3 to generate mullite at relatively high temperatures. Additionally, when the temperature exceeded 1,500 K, the molar percentages of Cu2O and CuO·Al2O3 rapidly increased, which was not conducive to the reduction of CuO. Figure 2(b) shows that when R (C/A) is 0.2, CaO combines with a part of the Al2O3 and SiO2 produced by the reduction reaction to form low-melting-point compounds, such as Ca aluminates and Ca silicates. With increasing temperature, the molar percentage of 3CaO·Al2O3·3SiO2 rapidly decreased; thereafter, it slightly increased; however, that of CaO·Al2O3·2SiO2 rapidly increased, and then, it remained constant. The molar percentages of CaO·Al2O3·SiO2, CaSiO3, and CaAl2SiO6 were less than 2.5%, and they increased first and then decreased. It indicated that the high temperature was favorable for forming the low-melting-point slag phase by combining CaO with Al2O3 and SiO2. Figure 2(c) indicates that when R (C/A) is 0.6, the molar percentages of Al2O3 and SiO2 in the slag phase significantly decrease, while those of CaO·Al2O3·2SiO2, CaSiO3, and CaAl2SiO6 further increase. Figure 2(d) shows that when R (C/A) is 1.0, the mole percentage of Al2O3 in the slag phase further decreases, while SiO2 and CaAl2SiO6 almost disappear, and Ca3Si2O7, 3CaO·2SiO2, CaO·2Al2O3, and CaO appear. It indicates that some CaO failed to combine with Al2O3 and SiO2 to form the low-melting-point slag phase and failed to play the role of slagging agent.

In conclusion, when CaO was added to the Al–Si–CuO–WO3 equilibrium system, with increasing R (C/A) , the phases of the slags gradually changed from Al silicates to Ca silicates and then to Ca silicates containing a high content of CaO and Ca aluminates, which is beneficial to reduce the melting point and viscosity [28]. Thus, the separation between metal and slag was promoted; however, a part of CaO did not play the role of a slagging agent when the CaO content was too high.

3.2 Effects on the CuW composites

Figure 3 shows the SEM images and elemental distribution of the CuW composites with different R (C/A) . The SEM images showed that the microstructure of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) primarily comprised a gray matrix, white particles, and black inclusions. The elemental distribution demonstrated that Cu was evenly distributed on the matrix, W and Si were distributed on the white particles, and Al was primarily distributed on the black spherical inclusions. Additionally, a small amount of Al and Si was distributed on the matrix. Figure 4(P1)–(P16) shows the EDS analysis results of phases P1–P16 presented in Figure 3. The results further demonstrated that the matrix (P1, P5, P9, P13) consisted of Cu, Al, and Si, and with the increase in R (C/A) , the Al content in the Cu matrix increased and that of Si decreased. The white particles comprised W particles (P2, P6, P10, P14) and W–Si intermetallic compounds (P3, P7, P11), and most of the W particles were surrounded by the W–Si intermetallic compounds. The atomic ratio of Si and W in the W–Si intermetallic compounds (P3, P7, P11) was approximately 2:1. From the phase diagram of the Si–W binary alloy [29], it was conjectured that it was a Si2W. When R (C/A) was 0 and 0.2, the black inclusions (P4, P8) mainly comprised Al and O, and the atomic ratio was approximately 2:3, which was inferred to be Al2O3. When R (C/A) was 0.6 and 1.0, the black inclusions (P12, P16) comprised Ca, Al, and O, which was inferred to be complex Ca aluminates. It was concluded that with the increase in the R (C/A) , the black inclusions gradually changed from high-melting-point Al2O3 to low-melting-point Ca aluminates, which was beneficial to the separation between the metal and slag and the reduction of inclusions.

Figure 3 SEM images (1,000×) and element distribution of the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).
Figure 3

SEM images (1,000×) and element distribution of the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).

Figure 4 EDS analysis results of the microstructure in the microalloying CuW composites presented in Figure 3.
Figure 4

EDS analysis results of the microstructure in the microalloying CuW composites presented in Figure 3.

To further analyze the microstructure of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) , Image-Pro Plus 6.0 was used to investigate the distribution of the phases, W particles, and inclusions.

Figure 5 shows the phase distribution of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . Without adding CaO, the area ratios of the matrix, W particles, Si2W, and inclusions were 29.02, 59.14, 9.44, and 2.40%, respectively. When the R (C/A) was 0.2, the area ratio of the Cu matrix, W particles, and inclusions decreased to 27.91, 56.12, and 0.88%, respectively, while that of Si2W significantly increased to 15.09%, which was conducive to the separation of the metal and slag. When R (C/A) was 0.6, the area ratio of the Cu matrix and Si2W increased to 30.36 and 16.89%, respectively. In this case, the addition of CaO further enhanced the separation of the metal and slag. When R (C/A) was 1.0, the area ratio of the Cu matrix, W particles, and inclusion increased to 31.31, 66.90, and 1.79%, respectively; however, the Si2W disappeared, indicating that the further increase in R (C/A) did not significantly enhance the separation of the metal and slag. In conclusion, when R (C/A) was 0.6, the separation effect was good.

Figure 5 Phase distribution of the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, d: 1.0).
Figure 5

Phase distribution of the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, d: 1.0).

Figure 6 shows the distribution of the phases containing W in the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . Without adding CaO, the average diameter of the phases containing W in the CuW composite was 5.04 µm, and the phases containing W were concentrated in 0–6.0 µm, and 7.11% was distributed in 10.0–14.0 µm. When the R (C/A) was 0.2, the average diameter of the W particles increased to 5.95 µm, the phases containing W were concentrated in 2.0–6.0 µm, and the concentration of the W particles distributed in 10.0–14.0 µm increased to 11.65%. When R (C/A) was 0.6, the average diameter of the W particles further increased to 6.32 µm, and the phases containing W were concentrated in 4.0–10.0 µm. When R (C/A) was 1.0, the average diameter of the W particles decreased to 5.77 µm, and the phases containing W were concentrated in 2.0–10.0 µm, and its distribution was more discrete. In conclusion, the average diameter of the phases containing W in the CuW composite increased when CaO was added to the raw material, and it increased first and then decreased with the increase in R (C/A) .

Figure 6 Distribution of the phases containing W in the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).
Figure 6

Distribution of the phases containing W in the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).

Figure 7 shows the distribution of inclusions in the metallographic structure of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . The results showed that without adding CaO, the average diameter of the inclusions in the CuW composites was 2.99 µm, the inclusions were mainly concentrated in 0–4.0 µm, and the inclusions above 6.0 µm accounted for 16.95%. After adding CaO, the inclusion particle size was still concentrated in 0–4.0 µm. When R (C/A) was 0.2, the average diameter of the inclusions increased to 3.81 µm, and the inclusions above 6.0 µm decreased to 15.89%. When R (C/A) was 0.6, the average diameter of the inclusions significantly decreased to 2.16 µm, and the inclusions above 6.0 µm rapidly decreased to 6.85%. When R (C/A) was 1.0, the average diameter of the inclusions slightly increased to 2.30 µm, and the inclusions above 6.0 µm continued to decrease to 6.01%. Thus, the average size of the inclusions in the CuW composites was the smallest when R (C/A) was 0.6, and the inclusions larger than 6.0 µm gradually decreased with the increase in R (C/A) , while those smaller than 4.0 µm remained unchanged. In conclusion, the removal effect of the inclusions larger than 6.0 µm is observed, while that of inclusions smaller than 4.0 µm is not observed.

Figure 7 Distribution of inclusions in the metallographic structure of the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).
Figure 7

Distribution of inclusions in the metallographic structure of the CuW composites prepared with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).

Table 1 shows the chemical composition of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . It is concluded that the content of W in the CuW composites prepared via the aluminothermic coupling with silicothermic reduction was lower than the target value of 50.0%. Without adding CaO, the contents of Si, Al, and O in the CuW composites were 9.40, 2.54, and 14.00%, respectively. After adding CaO, the Si content decreased, Al content increased, and O content decreased significantly. Furthermore, with the increase in R (C/A) , the contents of Si and O in the CuW composites gradually decreased, while those of Al and Ca gradually increased. The analysis presented in Figures 4 and 5 shows that O mainly exists in the form of oxides in the CuW composites. It can be concluded that the addition of CaO can significantly remove the oxide inclusions, and with increasing R (C/A) , the effect on the removal of inclusions was enhanced. Si mainly existed in the form of a solution and Si–W intermetallic compounds, while Al existed in the form of a solution and inclusions. It can be concluded that with the increase in R (C/A) , the decrease in the Si content occurred because the forward process of the silicothermic reduction reaction was significantly promoted by the combination of SiO2 and CaO, producing Ca silicates and hindering the formation of the Si–W intermetallic compounds.

Table 1

Composition of the CuW composites prepared with different R (C/A) , wt%

No. R (C/A) W Si Al O Ca Cu
A 0 32.45 9.40 2.54 14.00 0.02 Bal.
B 0.2 43.15 9.25 2.85 7.54 0.11 Bal.
C 0.6 46.38 6.98 3.84 3.92 0.23 Bal.
D 1.0 41.21 6.10 3.83 3.50 0.26 Bal.

Figure 8 shows the XRD patterns of the CuW composites obtained with different R (C/A) . It indicates that the diffraction peaks of W, Cu, and Si2W are observed. With an increase in R (C/A) , the diffraction peaks of W and Si2W gradually strengthened. This indicated that the addition of CaO is beneficial to improve the crystallinity of W and Si2W.

Figure 8 XRD patterns of the CuW composites obtained with different R (C/A) .
Figure 8

XRD patterns of the CuW composites obtained with different R (C/A) .

3.3 Effects on the metal–slag separation

Table 2 shows the chemical composition of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . The result showed that with the increase in R (C/A) , the content of SiO2 in the slags gradually decreased and the content of CaO gradually increased, which was mainly caused by the increased addition of CaO used as a slag former.

Table 2

Composition of the slags obtained with different R (C/A) , wt%

No. R (C/A) Al2O3 CuO WO3 SiO2 CaO Fe2O3 MgO Bal.
A 0 47.19 12.46 14.90 20.66 0.729 0.488 3.10 0.47
B 0.2 48.24 11.92 13.40 18.35 4.70 0.512 2.44 0.44
C 0.6 30.79 16.61 22.34 16.38 10.05 0.501 2.72 0.61
D 1.0 32.46 9.61 17.61 12.80 17.69 0.536 8.73 0.56

To investigate the effect of R (C/A) on the phases of the slags, XRD was used to analyze its phase composition. Figure 9 shows the XRD patterns of the slags obtained when the CuW composites were prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . Without adding CaO, the diffraction peaks of Al4.8O9.54Si1.2, SiO2, and Al2O3 are observed. After adding CaO, the diffraction peaks of CaWO4, CuAl2O4, and CaAl2Si2O8 appeared in the slags. With an increase in R (C/A) , the diffraction peaks of Al4.8O9.54Si1.2 and SiO2 gradually weakened and disappeared, whereas that of CaAl2Si2O8 strengthened. This indicated that the added CaO combined with the SiO2 and Al2O3 produced low-melting-point Ca aluminosilicates, which were beneficial to the separation of the metal and slag. However, CaO can easily combine with WO3 to form CaWO4. Additionally, Al12Ca8O32W2 and CuAl2O4 appeared in the slag when R (C/A) was relatively high. These by-products hindered the reduction process of the W oxides and reduced the reduction rate and recovery of W.

Figure 9 XRD patterns of the slags obtained with different R (C/A) .
Figure 9

XRD patterns of the slags obtained with different R (C/A) .

Figure 10 shows the metallographic photographs of the slags obtained when the CuW composites were prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) . The results showed that there were different-sized metal particles in the metallographic structure of the slags obtained with different R (C/A) . Without adding CaO, the metal particles in the slag were large, or the small metal particles were combined, which may be due to the high viscosity of the Al2O3–SiO2-based slag formed by the aluminothermic coupling with silicothermic reduction, which was not conducive to the reduction of metal particles during the separation of the metal and slag [30]. When R (C/A) was 0.2, the large metal particles disappeared and the number of small metal particles increased, which were evenly distributed in the slag, indicating that the viscosity and fluidity of the slag were changed. Furthermore, the separation effect of the metal and slag was promoted. When R (C/A) was 0.4 and 0.6, the number of small- and medium-sized metal particles decreased and these particles were dispersed in the slag. The results presented in Figure 9 show that the added CaO combined with SiO2 and Al2O3 produced low-melting-point Ca aluminosilicates, such as CaAl2Si2O8, and the viscosity and fluidity of the slag were further improved, during which the separation of the metal and slag was strengthened.

Figure 10 Metallographic photographs (200×) of the slags obtained with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).
Figure 10

Metallographic photographs (200×) of the slags obtained with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).

Figure 11 shows the distribution of the metal particles in the slags obtained with different R (C/A) . Without adding CaO, the average diameter of the metal particles in the slag was 1.63 µm, showing an F distribution. After adding CaO, with the increase in R (C/A) , the average diameter of the metal particles gradually decreased to 0.84 µm, and the proportion of the metal particles larger than 3.00 µm gradually decreased, while that of the particles smaller than 1.00 µm gradually increased. Furthermore, the distribution of the metal particles became concentrated. It indicates that the addition of CaO promoted the separation of the metal and slag, and the separation effect increased with the increase in R (C/A) . This was mainly due to the formation of the CaO–Al2O3–SiO2 slag. The ternary phase diagram of CaO–Al2O3–SiO2 system shows that the melting point CaO–Al2O3–SiO2 slag could be as low as 1,473 K, while the minimum melting point of CaO–Al2O3 slag is 1,668 K [31]. At the same time, research shows that the viscosity of CaO–Al2O3–SiO2 slag decreases with the increase in addition of CaO [28,32]. As a result, the addition of CaO may lead to a large decrease in the melting point and viscosity of the slag, which strengthened the separation effect of the metal and slag [33].

Figure 11 Distribution of the metal particles in the slags obtained with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).
Figure 11

Distribution of the metal particles in the slags obtained with different R (C/A) (a: 0, b: 0.2, c: 0.6, and d: 1.0).

4 Conclusions

The microstructure of the CuW composites prepared via the aluminothermic coupling with silicothermic reduction with different R (C/A) primarily comprised a Cu matrix, W particles, Si2W surrounding W particles, and a small number of inclusions. After adding CaO, the average particle size of the phases containing W increased, and it increased first and then decreased with the increase in R (C/A) . The addition of CaO affected the removal of large particles (≥6 µm) but not the removal of small particles (≤4 µm). With the increase in R (C/A) , the inclusions in the CuW composites gradually were transformed from high-melting-point Al2O3 to low-melting-point Ca aluminates, which was conducive to the separation of the metal and slag. The contents of Si and O in the CuW composites gradually decreased from 9.40 and 14.00% to 6.10 and 3.50%, while those of Al and Ca gradually increased from 2.54 and 0.02% to 3.83 and 0.26%, respectively.

  1. Funding information: This research was supported by the Natural Science Foundation of China (Grant No. 52204359), Chinese Postdoctoral Science Foundation (Grant No. 2022T150193), Natural Science Foundation of Henan Province (Grant No. 202400520123), Key Scientific Research Project of colleges and universities of Henan Province (Grant No. 22A450002), Doctoral Scientific Research Foundation of Henan University of Science and Technology (Grant No. 13480091), and Postdoctoral Scientific Research Foundation of Henan University of Science and Technology (Grant No. 13554020).

  2. Author contributions: All authors have accepted responsibility for the entire content of this manuscript and approved its submission.

  3. Conflict of interest: The authors state no conflict of interest.

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Received: 2022-07-31
Revised: 2022-11-18
Accepted: 2023-02-23
Published Online: 2023-03-16

© 2023 the author(s), published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/ntrev-2022-0527
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Artikel in diesem Heft

  1. Research Articles
  2. Preparation of CdS–Ag2S nanocomposites by ultrasound-assisted UV photolysis treatment and its visible light photocatalysis activity
  3. Significance of nanoparticle radius and inter-particle spacing toward the radiative water-based alumina nanofluid flow over a rotating disk
  4. Aptamer-based detection of serotonin based on the rapid in situ synthesis of colorimetric gold nanoparticles
  5. Investigation of the nucleation and growth behavior of Ti2AlC and Ti3AlC nano-precipitates in TiAl alloys
  6. Dynamic recrystallization behavior and nucleation mechanism of dual-scale SiCp/A356 composites processed by P/M method
  7. High mechanical performance of 3-aminopropyl triethoxy silane/epoxy cured in a sandwich construction of 3D carbon felts foam and woven basalt fibers
  8. Applying solution of spray polyurea elastomer in asphalt binder: Feasibility analysis and DSR study based on the MSCR and LAS tests
  9. Study on the chronic toxicity and carcinogenicity of iron-based bioabsorbable stents
  10. Influence of microalloying with B on the microstructure and properties of brazed joints with Ag–Cu–Zn–Sn filler metal
  11. Thermohydraulic performance of thermal system integrated with twisted turbulator inserts using ternary hybrid nanofluids
  12. Study of mechanical properties of epoxy/graphene and epoxy/halloysite nanocomposites
  13. Effects of CaO addition on the CuW composite containing micro- and nano-sized tungsten particles synthesized via aluminothermic coupling with silicothermic reduction
  14. Cu and Al2O3-based hybrid nanofluid flow through a porous cavity
  15. Design of functional vancomycin-embedded bio-derived extracellular matrix hydrogels for repairing infectious bone defects
  16. Study on nanocrystalline coating prepared by electro-spraying 316L metal wire and its corrosion performance
  17. Axial compression performance of CFST columns reinforced by ultra-high-performance nano-concrete under long-term loading
  18. Tungsten trioxide nanocomposite for conventional soliton and noise-like pulse generation in anomalous dispersion laser cavity
  19. Microstructure and electrical contact behavior of the nano-yttria-modified Cu-Al2O3/30Mo/3SiC composite
  20. Melting rheology in thermally stratified graphene-mineral oil reservoir (third-grade nanofluid) with slip condition
  21. Re-examination of nonlinear vibration and nonlinear bending of porous sandwich cylindrical panels reinforced by graphene platelets
  22. Parametric simulation of hybrid nanofluid flow consisting of cobalt ferrite nanoparticles with second-order slip and variable viscosity over an extending surface
  23. Chitosan-capped silver nanoparticles with potent and selective intrinsic activity against the breast cancer cells
  24. Multi-core/shell SiO2@Al2O3 nanostructures deposited on Ti3AlC2 to enhance high-temperature stability and microwave absorption properties
  25. Solution-processed Bi2S3/BiVO4/TiO2 ternary heterojunction photoanode with enhanced photoelectrochemical performance
  26. Electroporation effect of ZnO nanoarrays under low voltage for water disinfection
  27. NIR-II window absorbing graphene oxide-coated gold nanorods and graphene quantum dot-coupled gold nanorods for photothermal cancer therapy
  28. Nonlinear three-dimensional stability characteristics of geometrically imperfect nanoshells under axial compression and surface residual stress
  29. Investigation of different nanoparticles properties on the thermal conductivity and viscosity of nanofluids by molecular dynamics simulation
  30. Optimized Cu2O-{100} facet for generation of different reactive oxidative species via peroxymonosulfate activation at specific pH values to efficient acetaminophen removal
  31. Brownian and thermal diffusivity impact due to the Maxwell nanofluid (graphene/engine oil) flow with motile microorganisms and Joule heating
  32. Appraising the dielectric properties and the effectiveness of electromagnetic shielding of graphene reinforced silicone rubber nanocomposite
  33. Synthesis of Ag and Cu nanoparticles by plasma discharge in inorganic salt solutions
  34. Low-cost and large-scale preparation of ultrafine TiO2@C hybrids for high-performance degradation of methyl orange and formaldehyde under visible light
  35. Utilization of waste glass with natural pozzolan in the production of self-glazed glass-ceramic materials
  36. Mechanical performance of date palm fiber-reinforced concrete modified with nano-activated carbon
  37. Melting point of dried gold nanoparticles prepared with ultrasonic spray pyrolysis and lyophilisation
  38. Graphene nanofibers: A modern approach towards tailored gypsum composites
  39. Role of localized magnetic field in vortex generation in tri-hybrid nanofluid flow: A numerical approach
  40. Intelligent computing for the double-diffusive peristaltic rheology of magneto couple stress nanomaterials
  41. Bioconvection transport of upper convected Maxwell nanoliquid with gyrotactic microorganism, nonlinear thermal radiation, and chemical reaction
  42. 3D printing of porous Ti6Al4V bone tissue engineering scaffold and surface anodization preparation of nanotubes to enhance its biological property
  43. Bioinspired ferromagnetic CoFe2O4 nanoparticles: Potential pharmaceutical and medical applications
  44. Significance of gyrotactic microorganisms on the MHD tangent hyperbolic nanofluid flow across an elastic slender surface: Numerical analysis
  45. Performance of polycarboxylate superplasticisers in seawater-blended cement: Effect from chemical structure and nano modification
  46. Entropy minimization of GO–Ag/KO cross-hybrid nanofluid over a convectively heated surface
  47. Oxygen plasma assisted room temperature bonding for manufacturing SU-8 polymer micro/nanoscale nozzle
  48. Performance and mechanism of CO2 reduction by DBD-coupled mesoporous SiO2
  49. Polyarylene ether nitrile dielectric films modified by HNTs@PDA hybrids for high-temperature resistant organic electronics field
  50. Exploration of generalized two-phase free convection magnetohydrodynamic flow of dusty tetra-hybrid Casson nanofluid between parallel microplates
  51. Hygrothermal bending analysis of sandwich nanoplates with FG porous core and piezomagnetic faces via nonlocal strain gradient theory
  52. Design and optimization of a TiO2/RGO-supported epoxy multilayer microwave absorber by the modified local best particle swarm optimization algorithm
  53. Mechanical properties and frost resistance of recycled brick aggregate concrete modified by nano-SiO2
  54. Self-template synthesis of hollow flower-like NiCo2O4 nanoparticles as an efficient bifunctional catalyst for oxygen reduction and oxygen evolution in alkaline media
  55. High-performance wearable flexible strain sensors based on an AgNWs/rGO/TPU electrospun nanofiber film for monitoring human activities
  56. High-performance lithium–selenium batteries enabled by nitrogen-doped porous carbon from peanut meal
  57. Investigating effects of Lorentz forces and convective heating on ternary hybrid nanofluid flow over a curved surface using homotopy analysis method
  58. Exploring the potential of biogenic magnesium oxide nanoparticles for cytotoxicity: In vitro and in silico studies on HCT116 and HT29 cells and DPPH radical scavenging
  59. Enhanced visible-light-driven photocatalytic degradation of azo dyes by heteroatom-doped nickel tungstate nanoparticles
  60. A facile method to synthesize nZVI-doped polypyrrole-based carbon nanotube for Ag(i) removal
  61. Improved osseointegration of dental titanium implants by TiO2 nanotube arrays with self-assembled recombinant IGF-1 in type 2 diabetes mellitus rat model
  62. Functionalized SWCNTs@Ag–TiO2 nanocomposites induce ROS-mediated apoptosis and autophagy in liver cancer cells
  63. Triboelectric nanogenerator based on a water droplet spring with a concave spherical surface for harvesting wave energy and detecting pressure
  64. A mathematical approach for modeling the blood flow containing nanoparticles by employing the Buongiorno’s model
  65. Molecular dynamics study on dynamic interlayer friction of graphene and its strain effect
  66. Induction of apoptosis and autophagy via regulation of AKT and JNK mitogen-activated protein kinase pathways in breast cancer cell lines exposed to gold nanoparticles loaded with TNF-α and combined with doxorubicin
  67. Effect of PVA fibers on durability of nano-SiO2-reinforced cement-based composites subjected to wet-thermal and chloride salt-coupled environment
  68. Effect of polyvinyl alcohol fibers on mechanical properties of nano-SiO2-reinforced geopolymer composites under a complex environment
  69. In vitro studies of titanium dioxide nanoparticles modified with glutathione as a potential drug delivery system
  70. Comparative investigations of Ag/H2O nanofluid and Ag-CuO/H2O hybrid nanofluid with Darcy-Forchheimer flow over a curved surface
  71. Study on deformation characteristics of multi-pass continuous drawing of micro copper wire based on crystal plasticity finite element method
  72. Properties of ultra-high-performance self-compacting fiber-reinforced concrete modified with nanomaterials
  73. Prediction of lap shear strength of GNP and TiO2/epoxy nanocomposite adhesives
  74. A novel exploration of how localized magnetic field affects vortex generation of trihybrid nanofluids
  75. Fabrication and physicochemical characterization of copper oxide–pyrrhotite nanocomposites for the cytotoxic effects on HepG2 cells and the mechanism
  76. Thermal radiative flow of cross nanofluid due to a stretched cylinder containing microorganisms
  77. In vitro study of the biphasic calcium phosphate/chitosan hybrid biomaterial scaffold fabricated via solvent casting and evaporation technique for bone regeneration
  78. Insights into the thermal characteristics and dynamics of stagnant blood conveying titanium oxide, alumina, and silver nanoparticles subject to Lorentz force and internal heating over a curved surface
  79. Effects of nano-SiO2 additives on carbon fiber-reinforced fly ash–slag geopolymer composites performance: Workability, mechanical properties, and microstructure
  80. Energy bandgap and thermal characteristics of non-Darcian MHD rotating hybridity nanofluid thin film flow: Nanotechnology application
  81. Green synthesis and characterization of ginger-extract-based oxali-palladium nanoparticles for colorectal cancer: Downregulation of REG4 and apoptosis induction
  82. Abnormal evolution of resistivity and microstructure of annealed Ag nanoparticles/Ag–Mo films
  83. Preparation of water-based dextran-coated Fe3O4 magnetic fluid for magnetic hyperthermia
  84. Statistical investigations and morphological aspects of cross-rheological material suspended in transportation of alumina, silica, titanium, and ethylene glycol via the Galerkin algorithm
  85. Effect of CNT film interleaves on the flexural properties and strength after impact of CFRP composites
  86. Self-assembled nanoscale entities: Preparative process optimization, payload release, and enhanced bioavailability of thymoquinone natural product
  87. Structure–mechanical property relationships of 3D-printed porous polydimethylsiloxane films
  88. Nonlinear thermal radiation and the slip effect on a 3D bioconvection flow of the Casson nanofluid in a rotating frame via a homotopy analysis mechanism
  89. Residual mechanical properties of concrete incorporated with nano supplementary cementitious materials exposed to elevated temperature
  90. Time-independent three-dimensional flow of a water-based hybrid nanofluid past a Riga plate with slips and convective conditions: A homotopic solution
  91. Lightweight and high-strength polyarylene ether nitrile-based composites for efficient electromagnetic interference shielding
  92. Review Articles
  93. Recycling waste sources into nanocomposites of graphene materials: Overview from an energy-focused perspective
  94. Hybrid nanofiller reinforcement in thermoset and biothermoset applications: A review
  95. Current state-of-the-art review of nanotechnology-based therapeutics for viral pandemics: Special attention to COVID-19
  96. Solid lipid nanoparticles for targeted natural and synthetic drugs delivery in high-incidence cancers, and other diseases: Roles of preparation methods, lipid composition, transitional stability, and release profiles in nanocarriers’ development
  97. Critical review on experimental and theoretical studies of elastic properties of wurtzite-structured ZnO nanowires
  98. Polyurea micro-/nano-capsule applications in construction industry: A review
  99. A comprehensive review and clinical guide to molecular and serological diagnostic tests and future development: In vitro diagnostic testing for COVID-19
  100. Recent advances in electrocatalytic oxidation of 5-hydroxymethylfurfural to 2,5-furandicarboxylic acid: Mechanism, catalyst, coupling system
  101. Research progress and prospect of silica-based polymer nanofluids in enhanced oil recovery
  102. Review of the pharmacokinetics of nanodrugs
  103. Engineered nanoflowers, nanotrees, nanostars, nanodendrites, and nanoleaves for biomedical applications
  104. Research progress of biopolymers combined with stem cells in the repair of intrauterine adhesions
  105. Progress in FEM modeling on mechanical and electromechanical properties of carbon nanotube cement-based composites
  106. Antifouling induced by surface wettability of poly(dimethyl siloxane) and its nanocomposites
  107. TiO2 aerogel composite high-efficiency photocatalysts for environmental treatment and hydrogen energy production
  108. Structural properties of alumina surfaces and their roles in the synthesis of environmentally persistent free radicals (EPFRs)
  109. Nanoparticles for the potential treatment of Alzheimer’s disease: A physiopathological approach
  110. Current status of synthesis and consolidation strategies for thermo-resistant nanoalloys and their general applications
  111. Recent research progress on the stimuli-responsive smart membrane: A review
  112. Dispersion of carbon nanotubes in aqueous cementitious materials: A review
  113. Applications of DNA tetrahedron nanostructure in cancer diagnosis and anticancer drugs delivery
  114. Magnetic nanoparticles in 3D-printed scaffolds for biomedical applications
  115. An overview of the synthesis of silicon carbide–boron carbide composite powders
  116. Organolead halide perovskites: Synthetic routes, structural features, and their potential in the development of photovoltaic
  117. Recent advancements in nanotechnology application on wood and bamboo materials: A review
  118. Application of aptamer-functionalized nanomaterials in molecular imaging of tumors
  119. Recent progress on corrosion mechanisms of graphene-reinforced metal matrix composites
  120. Research progress on preparation, modification, and application of phenolic aerogel
  121. Application of nanomaterials in early diagnosis of cancer
  122. Plant mediated-green synthesis of zinc oxide nanoparticles: An insight into biomedical applications
  123. Recent developments in terahertz quantum cascade lasers for practical applications
  124. Recent progress in dielectric/metal/dielectric electrodes for foldable light-emitting devices
  125. Nanocoatings for ballistic applications: A review
  126. A mini-review on MoS2 membrane for water desalination: Recent development and challenges
  127. Recent updates in nanotechnological advances for wound healing: A narrative review
  128. Recent advances in DNA nanomaterials for cancer diagnosis and treatment
  129. Electrochemical micro- and nanobiosensors for in vivo reactive oxygen/nitrogen species measurement in the brain
  130. Advances in organic–inorganic nanocomposites for cancer imaging and therapy
  131. Advancements in aluminum matrix composites reinforced with carbides and graphene: A comprehensive review
  132. Modification effects of nanosilica on asphalt binders: A review
  133. Decellularized extracellular matrix as a promising biomaterial for musculoskeletal tissue regeneration
  134. Review of the sol–gel method in preparing nano TiO2 for advanced oxidation process
  135. Micro/nano manufacturing aircraft surface with anti-icing and deicing performances: An overview
  136. Cell type-targeting nanoparticles in treating central nervous system diseases: Challenges and hopes
  137. An overview of hydrogen production from Al-based materials
  138. A review of application, modification, and prospect of melamine foam
  139. A review of the performance of fibre-reinforced composite laminates with carbon nanotubes
  140. Research on AFM tip-related nanofabrication of two-dimensional materials
  141. Advances in phase change building materials: An overview
  142. Development of graphene and graphene quantum dots toward biomedical engineering applications: A review
  143. Nanoremediation approaches for the mitigation of heavy metal contamination in vegetables: An overview
  144. Photodynamic therapy empowered by nanotechnology for oral and dental science: Progress and perspectives
  145. Biosynthesis of metal nanoparticles: Bioreduction and biomineralization
  146. Current diagnostic and therapeutic approaches for severe acute respiratory syndrome coronavirus-2 (SARS-COV-2) and the role of nanomaterial-based theragnosis in combating the pandemic
  147. Application of two-dimensional black phosphorus material in wound healing
  148. Special Issue on Advanced Nanomaterials and Composites for Energy Conversion and Storage - Part I
  149. Helical fluorinated carbon nanotubes/iron(iii) fluoride hybrid with multilevel transportation channels and rich active sites for lithium/fluorinated carbon primary battery
  150. The progress of cathode materials in aqueous zinc-ion batteries
  151. Special Issue on Advanced Nanomaterials for Carbon Capture, Environment and Utilization for Energy Sustainability - Part I
  152. Effect of polypropylene fiber and nano-silica on the compressive strength and frost resistance of recycled brick aggregate concrete
  153. Mechanochemical design of nanomaterials for catalytic applications with a benign-by-design focus
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Heruntergeladen am 8.9.2025 von https://www.degruyterbrill.com/document/doi/10.1515/ntrev-2022-0527/html
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